CN103432997B - Cu base organic backbone-graphene oxide composite porous material and preparation method thereof - Google Patents
Cu base organic backbone-graphene oxide composite porous material and preparation method thereof Download PDFInfo
- Publication number
- CN103432997B CN103432997B CN201310390975.5A CN201310390975A CN103432997B CN 103432997 B CN103432997 B CN 103432997B CN 201310390975 A CN201310390975 A CN 201310390975A CN 103432997 B CN103432997 B CN 103432997B
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- porous material
- composite porous
- oxide composite
- organic backbone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The invention belongs to metal-organic framework materials technical field, disclose a kind of Cu base organic backbone-graphene oxide composite porous material and its preparation method and application.The method comprises following concrete steps: Schweinfurt green, 1,3,5-benzenetricarboxylic acid and graphene oxide are mixed, ball milling, washing, centrifugal, dries, obtains Cu base organic backbone-graphene oxide composite porous material.Preparation method of the present invention, having the advantages such as reaction time short (only needing 30min), solvent-free, preparation amount are large, the low and method of operating of consuming energy is simple, is the novel green synthetic method of a kind of high-efficiency cleaning, environmental protection close friend.The Cu base organic backbone that the present invention obtains-adsorption capacity of graphene oxide composite porous material to hydro carbons VOCs significantly improves, under equal conditions, be 2.06 times of Na-ZSM molecular sieve to the adsorbance of methyl alcohol, 2.54 times of flexibility-MOF (E), 1.79 times of HKUST-1.
Description
Technical field
The invention belongs to metal-organic framework materials technical field, particularly a kind of Cu base organic backbone-graphene oxide composite porous material and its preparation method and application.
Background technology
Metal-organic framework materials (Metal Organic Frameworks is called for short MOFs) is by containing the multiple tooth organic ligand of oxygen, nitrogen etc. and the class zeolitic frameworks material having special pore passage structure of transition metal ions self assembly.It has the advantage that traditional sorbing material does not have: (I) porosity is high, specific area is huge; (II) high thermal stability; (III) pore structure is regular, and pore size design is controlled; (IV) surface chemistry group modified adjustable.Because MOFs material has the physical and chemical performance of above uniqueness, the various fields such as it is separated in gas storage, gas absorption, selective and chiral catalyst, microreactor, molecular recognition, drug delivery, photoelectric properties application are made all to have tempting potential application foreground, cause the great interest of numerous researcher, thus the MOFs material technology method of Design and synthesis different structure and performance is developed rapidly.
In new MOFs design of material, in order to improve absorption property and the mechanical performance of MOFs material, people utilize MOFs unit and inorganic material or organic material to carry out composite design to go out novel MOFs composite.Had by the attainable effect of compound: (1) MOFs composite absorption property is significantly improved; (2) mechanical performance is improved, and MOFs material is convenient to shaping, is beneficial to practical engineering application.The Zn atom generation bonding action in ZnO4 bunch in hydrogen atom on the hydroxyl on graphite oxide individual layer edge and MOF-5 crystal is utilized as people [1] such as Camille Petit, prepare MOF-5/ graphite oxide composite porous material, relative to MOF-5 material, the absorption property of this composite to hydrogen sulfide and ammonia is improved; Marcus Rose [2] is by MIL-100 metal-organic framework materials and different organic material (as: polystyrene, polyvinylpyrrolidone, polyacrylonitrile, polypropylene) carry out compound, the MOF/ polymer composites prepared, its mechanical stability is all higher than MIL-100 metal-organic framework materials.
In synthetic technology, MOFs material and composite synthesis thereof mainly contain water (solvent) hot method, liquid phase diffusion method, microwave method, ultrasonic method etc., wherein, the hot method synthesis of water (solvent) more often uses, but water (solvent) hot method generated time is longer, usually need tens hours even a couple of days.Although microwave method, ultrasonic method etc. after improving decrease the time of reaction; but these synthetic methods all need to consume a large amount of expensive organic solvent; as dimethyl formamide (DMF), DEF (DEF) etc.; and reclaim difficulty; MOFs manufacture of materials cost is caused to remain high; also easily cause the secondary pollution to environment simultaneously, relate to environmental problem, safety problem and energy problem, therefore these methods are difficult to the industrial scale production realizing metal-organic framework materials.Therefore the preparation method seeking a kind of high-efficiency cleaning, eco-friendly metallic organic framework and composite thereof has important practical significance.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art with not enough, primary and foremost purpose of the present invention is the preparation method providing a kind of Cu base organic backbone-graphene oxide composite porous material.The method adopts mechanochemical reaction, and namely mechanical force (energy) is brought out and promoted that between metal ion and organic ligand, chemical complexing occurring reacts, and accelerates the formation of metal-organic framework materials pore structure.The advantages such as this synthetic method is simple, have reaction time short, solvent-free or trace solvent, preparation amount is large, it is low to consume energy and method of operating is simple are the novel method for synthesizing of a kind of high-efficiency cleaning, environmental protection and energy saving.
Another object of the present invention is the Cu base organic backbone-graphene oxide composite porous material providing said method to prepare.Cu base organic backbone-graphene oxide composite porous material prepared by the present invention, due to graphene oxide aspect chemical functional group and the unsaturated Cu in MOFs unit
2+there is bonding, formed composite porous; Meanwhile, due to the intercalation of graphene oxide, dispersion force can be produced on MOFs unit and Graphene individual layer interface, thus there is higher absorption property.
Still a further object of the present invention is to provide above-mentioned Cu base organic backbone-graphene oxide composite porous material preparing the application in sorbing material.
Object of the present invention is realized by following proposal:
A preparation method for Cu base organic backbone-graphene oxide composite porous material, comprises following concrete steps:
Schweinfurt green, 1,3,5-benzenetricarboxylic acid and graphene oxide are mixed, ball milling, washing, centrifugal, dry, obtain Cu base organic backbone-graphene oxide composite porous material.
Schweinfurt green used (Cu (CH
3cOO)
2h
2o) and the mol ratio of 1,3,5-benzenetricarboxylic acid be (1 ~ 2): 1.
The amount of graphene oxide used is 2 ~ 8% of Schweinfurt green and 1,3,5-benzenetricarboxylic acid gross mass.Graphene oxide deposits effect both ways: on the one hand due to the intercalation of graphene oxide, can produce dispersion force on MOFs unit and Graphene individual layer interface, this dispersion force can increase the interaction force of the functional group of adsorption activity position (metal ion) in adsorbate (alkane molecule) and metallic organic framework or organic ligand; There is epoxy radicals and hydroxyl in graphene oxide interlayer in addition, these group meetings and with the unsaturated Cu in MOFs unit
2+there is bonding, form loose structure, simultaneously these groups can improve a lot to the adsorption capacity of alcohols VOC material (can and alcohols on hydroxyl formation hydrogen bond).If the consumption of graphene oxide is too small, the advantage display of Graphene is not out; If the consumption of graphene oxide is excessive, excessive graphene oxide will block the hole of porous material, serious surface area and the pore volume reducing material, and then reduces adsorption capacity.
The condition of described ball milling is ball milling 30 ~ 60min under 1100 ~ 1230r/min.
Preferably, the condition of described ball milling is ball milling 30min under 1230r/min.
If rotational speed of ball-mill is excessive, the skeleton structure that material synthesizes in preparation process is easily caved in, and destroys structure and the performance of material; If rotating speed is too small, skeleton can not be provided to form the energy needed, be difficult to obtain composite porous material, and required time is long.
Described washing refers to use ethanol water and chloroform successively.
In ethanol water used, the volume ratio of second alcohol and water is (1 ~ 2): 1.
Wash with the aqueous solution of ethanol: Schweinfurt green (Cu (CH3COO) 2H2O) residual in course of reaction and the acetic acid molecule generated can be dissolved in water to be removed; Organic acid 1,3, the 5-benzenetricarboxylic acid existed with guest molecule in unreacted and Cu base organic backbone-graphene oxide composite porous material skeleton dissolves and removes in ethanol.
Wash with chloroform: be to remove further to be present in 1,3,5-benzenetricarboxylic acid in stephanoporate framework material with guest molecule.
Described centrifugal rotating speed is 5000 ~ 7000r/min.
Described oven dry refers to middle blowing-type drying box, and temperature is be baked to drying at 100 ~ 180 DEG C.
Cu base organic backbone-graphene oxide composite porous material of the present invention will subside on 250 ~ 300 DEG C of structures, and therefore baking temperature will control below 250 DEG C.
Cu base organic backbone-graphene oxide composite porous material that said method prepares.
Above-mentioned Cu base organic backbone-graphene oxide composite porous material is preparing the application in sorbing material.
Mechanism of the present invention is:
The present invention is utilize the chemical effect that mechanical force (energy) produces by mechanochemical reaction synthesis Cu base organic backbone-graphene oxide composite porous material, reduces Schweinfurt green (Cu (CH
3cOO)
2h
2o) and the activation energy that reacts to each other between 1,3,5-benzenetricarboxylic acid, form nucleus or the crystallization of noval chemical compound, chemical reaction occurs; By adding graphene oxide, graphene oxide aspect chemical functional is impelled to roll into a ball and the unsaturated Cu in MOFs unit
2+there is bonding, accelerate the formation of metal-organic framework materials pore structure, finally prepare Cu base organic backbone-graphene oxide composite porous material, and give excellent absorption property.
The present invention, relative to prior art, has following advantage and beneficial effect:
(1) the present invention utilizes the chemical effect that mechanical force (energy) produces, and react to each other between reduction Schweinfurt green and 1,3,5-benzenetricarboxylic acid activation energy, forms nucleus or the crystallization of noval chemical compound, chemical reaction occurs; By adding graphene oxide, graphene oxide aspect chemical functional is impelled to roll into a ball and the unsaturated Cu in MOFs unit
2+there is bonding, accelerate the formation of metal-organic framework materials pore structure, finally prepare Cu base organic backbone-graphene oxide composite porous material, and give excellent absorption property.Preparation method of the present invention, having reaction time short (only needing 30min), solvent-free, preparation amount large (can reach feather weight), consume energy low (not needing heating) and the advantage such as method of operating is simple, is the novel green synthetic method of a kind of high-efficiency cleaning, environmental protection close friend.
(2) existing sorbing material is contrasted, the Cu base organic backbone that the present invention obtains-adsorption capacity of graphene oxide composite porous material to hydro carbons VOCs significantly improves, under equal conditions, Cu base organic backbone-graphene oxide composite porous material of the present invention is 2.06 times of Na-ZSM molecular sieve to the adsorbance of methyl alcohol, 2.01 times of NENU-3 molecular sieve, 2.54 times of flexibility-MOF (E), 2.05 times of flexibility-MOF (M), 1.79 times of HKUST-1.
(3) XRD spectra of Cu base organic backbone-graphene oxide composite porous material that obtains of the present invention and the Cu base organic framework material basic simlarity of non-oxidized graphite alkene compound, the skeleton structure and pore structure that retain original metallo organic material are described, micro-Double hole skeleton structure in having, micropore is beneficial to the strong suction-operated to adsorption molecule material, has the adsorption and diffusion that more mesopore is beneficial to adsorption molecule simultaneously.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of the porous material that embodiment 1 ~ 4 prepares.
Fig. 2 is the methanol adsorption isollaothermic chart of the porous material that embodiment 1 ~ 4 prepares.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1: comparative example
By 1.204g Cu (CH
3cOO)
2h
2o and 0.808g1,3, stainless steel jar mill put into by 5-benzenetricarboxylic acid, adds stainless steel ball-milling pearl, puts into ball mill, then at 1100r/min(42.97Hz) ball milling 30 ~ 45min under condition, after gained pressed powder being carried out successively ethanol water (ethanol: water is 1:1) and chloroform, 5000 ~ 7000r/min centrifugal filtration, obtains product, put at 100 ~ 180 DEG C, baking oven and dry, and to mark this sample be HKUST-1.
The preparation of embodiment 2:Cu base organic backbone-graphene oxide composite porous material
By 1.204g Cu (CH
3cOO)
2h
2stainless steel jar mill put into by O and 1.144g1,3,5-benzenetricarboxylic acid, and then adding 0.0470g graphene oxide (is Cu (CH
3cOO)
2h
2o and 1,3,2% of 5-benzenetricarboxylic acid gross mass), and mix, add stainless steel ball-milling pearl, put into ball mill, then at 1150r/min(46.75Hz) ball milling 45min under condition, after the aqueous solution (ethanol: water is 1:1) gained pressed powder being carried out successively ethanol and chloroform, product is extracted in 5000 ~ 7000r/min centrifugal filtration, product puts into the oven dry of 100 ~ 180 DEG C, baking oven, and to mark this sample be HKUST-GO-2.
The preparation of embodiment 3:Cu base organic backbone-graphene oxide composite porous material
By 1.701g Cu (CH
3cOO)
2h
2stainless steel jar mill put into by O and 0.808g1,3,5-benzenetricarboxylic acid, and then adding 0.125g graphene oxide (is Cu (CH
3cOO)
2h
2o and 1,3,5% of 5-benzenetricarboxylic acid gross mass), and mix, add stainless steel ball-milling pearl, put into ball mill, then at 1100r/min(42.97Hz) ball milling 60min under condition, after the aqueous solution (ethanol: water is 2:1) gained pressed powder being carried out successively ethanol and chloroform, product is extracted in 5000 ~ 7000r/min centrifugal filtration, product puts into the oven dry of 100 ~ 180 DEG C, baking oven, and to mark this sample be HKUST-GO-5.
The preparation of embodiment 4:Cu base organic backbone-graphene oxide composite porous material
By 1.204g Cu (CH
3cOO)
2h
2stainless steel jar mill put into by O and 0.808g1,3,5-benzenetricarboxylic acid, and then adding 0.161g graphene oxide (is Cu (CH
3cOO)
2h
2o and 1,3,8% of 5-benzenetricarboxylic acid gross mass), and mix, add stainless steel ball-milling pearl, put into ball mill, then 1230r/min(50Hz) ball milling 30min under condition, after the aqueous solution (ethanol: water is 1:1) gained pressed powder being carried out successively ethanol and chloroform, product is extracted in 5000 ~ 7000r/min centrifugal filtration, product puts into the oven dry of 100 ~ 180 DEG C, baking oven, and to mark this sample be HKUST-GO-8.
The performance measurement of embodiment 5:Cu base organic backbone-graphene oxide composite porous material
(1) the pore structure character of porous material measures
Adopt the pore structure of ASAP-2020M specific surface pore-size distribution instrument to the porous material that embodiment 1 ~ 4 prepares to characterize, result as shown in Tables 1 and 2.
The specific area parameter of table 1 porous material
The pore volume of table 2 porous material and aperture parameters
As can be seen from table 1,2, prepared by the present invention, the BET specific surface area of HKUST-1 metal-organic framework materials is 940.6m
2/ g.The metal-organic framework materials prepared of the inventive method not only specific area is large, and generated time extremely short (minute meter), there is fairly obvious advantage.The BET specific surface area of the Cu base organic backbone-graphene oxide composite porous material prepared by the present invention is about 1045 ~ 1203m
2between/g, and along with the increase surface area of GO compound quantity first reduces rear increase, simultaneously due to MOFs unit and Graphene individual layer interface producing dispersion force, this dispersion force can increase the interaction force of the functional group of adsorption activity position (metal ion) in adsorbate (alkane molecule) and metallic organic framework or organic ligand; There is epoxy radicals and hydroxyl in graphene oxide interlayer in addition, these group meetings and with the unsaturated Cu in MOFs unit
2+there is bonding, thus define more micropore.The Micropore volume of the Cu base organic backbone-graphene oxide composite porous material prepared by the present invention is made first to reduce rear increase along with the increase of GO compound quantity.Total pore volume is 0.7658cm to the maximum
3/ g, Micropore volume is 0.4699cm to the maximum
3/ g, wherein mesopore pore size is about about 7 ~ 10nm, illustrates that the porous material that embodiment 1 ~ 4 prepares all has higher specific area and pore volume, and has relatively-stationary micropore and mesopore pore size skeleton structure.Cu base organic backbone-graphene oxide composite porous material has a large amount of middle microcellular structures, micro-Double hole skeleton structure in having, and micropore is beneficial to the strong suction-operated to adsorption molecule material, has the adsorption and diffusion that more mesopore is beneficial to adsorption molecule simultaneously.
(2) crystal structure properties of Cu base organic backbone-graphene oxide composite porous material
The crystal structure of D8-ADVANCE model X-ray diffractometer to the porous material that the embodiment of the present invention 1 ~ 4 prepares adopting German Bruker company to produce characterizes respectively, graphene oxide (GO) is as blank, wherein operating condition is: copper target, 40KV, 40mA, step-length 0.02 degree, sweep speed 17.7 seconds/step.
As can be seen from Figure 1, three kinds of Cu base organic backbone-graphene oxide composite porous materials and HKUST-1 sample all have identical XRD spectra, and its principal character peak position is identical, and peak is strong and sharp-pointed, under this illustrates four kinds of conditions, synthesized material has identical crystal structure, and crystalline framework is stablized.
(3) Cu base organic backbone-graphene oxide composite porous material and HKUST-1 porous material are to the absorption property of methyl alcohol
The IGA-003 type intelligent gravimetric instrument adopting Hiden company of Britain to produce measures adsorption isotherm.Fig. 2 is 298K, and under different pressures, the adsorption isotherm on the porous material that methyl alcohol prepares in embodiment 1 ~ 4, the pretreatment condition before sample test is: at 150 DEG C, sample is vacuumized dry 8h, and vacuum is 3 ~ 5Pa.
Shown by Fig. 2, the HKUST-1 that embodiment 1 prepares is 4.846mmol/g to the equilibrium adsorption capacity of methyl alcohol, and synthesis only needs 30 minutes, than the HKUST-1 porous material (Ma of hydro-thermal method reaction 20h synthesis, F.J., et al., Adsorption of volatile organic compounds in porous metal-organic frameworks functionalized by polyoxometalates.JOURNAL OF SOLID STATE CHEMISTRY, 2011.184 (11): p.3034-3039.) there is higher adsorbance.And hydro-thermal method needs to use a large amount of alcohol solvents, and HKUST-1 building-up process of the present invention does not use solvent, and generated time shortens, and it is improved to the adsorption capacity of methyl alcohol.
Also can be found out by Fig. 2, under 298K, HKUST-GO-2, HKUST-GO-5, HKUST-GO-8 and HKUST-1 porous material is the preferential adsorption curve of I type to the adsorption isotherm of methyl alcohol, be mainly micro-porous adsorption, because graphene oxide interlayer exists epoxy radicals and hydroxyl, these group meetings and with the unsaturated Cu in MOFs unit
2+there is bonding, thus define more micropore.The Micropore volume of the Cu base organic backbone-graphene oxide composite porous material prepared by the present invention is improved largely relative to HKSUT-1 porous material, therefore the adsorbance of composite porous material to methyl alcohol significantly improves, and its saturated extent of adsorption increases about 70%.Micro-double-pore structure during the porous material of the embodiment of the present invention 1 ~ 4 all has, simultaneously due to the intercalation of graphene oxide, dispersion force can be produced on MOFs unit and Graphene individual layer interface, this dispersion force can increase the interaction force of the functional group of adsorption activity position (metal ion) in adsorbate (alkane molecule) and metallic organic framework or organic ligand, thus improves the absorption property of Cu Base Metal organic backbone-graphene oxide composite porous material.Make Cu base organic backbone-graphene oxide composite porous material obtained by the present invention to the adsorbance of methyl alcohol far above the adsorbance of HKUST-1 to methyl alcohol.
Table 3 is methyl alcohol adsorption phase nanoreactor data on different sorbing material.As can be seen from the table, under equal conditions, HKUST-GO-8 is 2.06 times of Na-ZSM molecular sieve to the adsorbance of methyl alcohol, 2.01 times of NENU-3 molecular sieve, 2.54 times of flexibility-MOF (E), 2.05 times of flexibility-MOF (M), HKUST-1(hydro-thermal method) 1.79 times.Cu base organic backbone-graphene oxide composite porous material that the inventive method synthesizes shows excellent absorption property to methyl alcohol.
The adsorbance of table 3 methyl alcohol on different sorbing material
Meanwhile, the synthetic method of Cu base organic backbone-graphene oxide composite porous material provided by the invention, due to not with an organic solvent; generated time is short; efficiency is high, and being easy to large-scale industrial and producing, is a kind of clean and effective, eco-friendly porous material preparation method.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from Spirit Essence of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (7)
1. the preparation method of Cu base organic backbone-graphene oxide composite porous material, it is characterized in that comprising following concrete steps: by Schweinfurt green, 1,3,5-benzenetricarboxylic acid and graphene oxide mix, ball milling, washing, centrifugal, dry, obtain Cu base organic backbone-graphene oxide composite porous material;
The mol ratio of Schweinfurt green used and 1,3,5-benzenetricarboxylic acid is (1 ~ 2): 1;
The amount of graphene oxide used is 2 ~ 8 % of Schweinfurt green and 1,3,5-benzenetricarboxylic acid gross mass;
The condition of described ball milling is ball milling 30 ~ 60 min under 1100 ~ 1230 r/min.
2. the preparation method of Cu base organic backbone-graphene oxide composite porous material according to claim 1, is characterized in that: the condition of described ball milling is ball milling 30 min under 1230 r/min.
3. the preparation method of Cu base organic backbone-graphene oxide composite porous material according to claim 1, is characterized in that: described washing refers to use ethanol water and chloroform successively.
4. the preparation method of Cu base organic backbone-graphene oxide composite porous material according to claim 3, is characterized in that: in ethanol water used, the volume ratio of second alcohol and water is (1 ~ 2): 1.
5. the preparation method of Cu base organic backbone-graphene oxide composite porous material according to claim 1, is characterized in that: described centrifugal rotating speed is 5000 ~ 7000 r/min; Described oven dry refers to middle blowing-type drying box, and temperature is be baked to drying at 100 ~ 180 DEG C.
6. the Cu base organic backbone-graphene oxide composite porous material wanting the preparation method of the Cu base organic backbone-graphene oxide composite porous material described in 1 ~ 5 any one to prepare according to right.
7. Cu base organic backbone-graphene oxide composite porous material according to claim 6 is preparing the application in sorbing material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310390975.5A CN103432997B (en) | 2013-08-30 | 2013-08-30 | Cu base organic backbone-graphene oxide composite porous material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310390975.5A CN103432997B (en) | 2013-08-30 | 2013-08-30 | Cu base organic backbone-graphene oxide composite porous material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103432997A CN103432997A (en) | 2013-12-11 |
| CN103432997B true CN103432997B (en) | 2015-09-02 |
Family
ID=49686766
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310390975.5A Active CN103432997B (en) | 2013-08-30 | 2013-08-30 | Cu base organic backbone-graphene oxide composite porous material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103432997B (en) |
Families Citing this family (34)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103736523B (en) * | 2014-01-10 | 2016-01-20 | 南京工业大学 | A kind of High-stability metal organic skeleton composite, preparation method and application thereof |
| CN104138746A (en) * | 2014-07-22 | 2014-11-12 | 华南理工大学 | Copper-based metal-organic framework porous material and preparation method and application thereof |
| CN104201385B (en) * | 2014-08-14 | 2016-07-06 | 中国科学技术大学 | The preparation method of a kind of high nitrogen doped class graphene nano particle and the application as lithium ion battery negative material thereof |
| CN104226256B (en) * | 2014-08-14 | 2017-02-15 | 华南理工大学 | Spherical forming Cu base metal organic skeleton-graphene oxide composite material and preparation method of spherical forming Cu base metal organic skeleton-graphene oxide composite material |
| CN104592255B (en) * | 2014-12-10 | 2016-10-05 | 华南理工大学 | A kind of method repairing cuprio-metallic organic framework porous material |
| CN105107462A (en) * | 2015-07-28 | 2015-12-02 | 沈阳理工大学 | Preparation method for oxidized graphene-metal organic framework nano composite material |
| CN105170095B (en) * | 2015-09-16 | 2017-10-20 | 华南理工大学 | A kind of In bases organic backbone graphene oxide composite material and its preparation method and application |
| CN105253896A (en) * | 2015-09-17 | 2016-01-20 | 上海大学 | Preparation method for graphene-4A type molecular sieve composite material |
| CN106622151B (en) * | 2015-11-03 | 2019-04-12 | 中国石油化工股份有限公司 | Composite material and preparation method and application containing metal-organic framework materials |
| CN105734038A (en) * | 2016-01-22 | 2016-07-06 | 南京工业大学 | Enzyme-GO-MOFs nano composite catalyst and preparation method thereof |
| CN106076260A (en) * | 2016-06-15 | 2016-11-09 | 华南理工大学 | A kind of room temperature fast preparation method of metallic organic framework oxidized graphite composite material |
| CN106040181A (en) * | 2016-07-19 | 2016-10-26 | 蚌埠学院 | Metal organic framework material NH2-MIL-53(Al), preparation method and application |
| CN106256432A (en) * | 2016-08-03 | 2016-12-28 | 江苏大学 | A kind of water oxidation reaction catalyst based on metallic organic framework graphene oxide and preparation method thereof |
| US11478774B2 (en) | 2016-08-29 | 2022-10-25 | Cornell University | Metal organic frameworks and methods of making and using same |
| CN106362691A (en) * | 2016-10-31 | 2017-02-01 | 扬州大学 | Method for preparing graphene oxide/molecular sieve composite adsorption material |
| CN106450590B (en) * | 2016-11-04 | 2019-03-01 | 中南大学 | A kind of copper/porous fibrous carbon material of nitrogen codope, preparation method and applications |
| CN106669608B (en) * | 2016-12-21 | 2019-10-29 | 南京工业大学 | A kind of graphene oxide package metal-organic framework materials and preparation method thereof |
| CN106861636B (en) * | 2017-03-20 | 2018-06-22 | 中国石油大学(华东) | A kind of metal organic coordination polymer adsorbent refined for fuel oil and regeneration method |
| CN107158964B (en) * | 2017-07-04 | 2020-03-03 | 中国石油大学(华东) | Composite membrane material based on metal organic framework nanosheets and graphene oxide, preparation method and application in gas separation |
| CN107589159B (en) * | 2017-09-05 | 2019-06-25 | 济南大学 | A kind of preparation method and application of chirality MOF nanofiber-graphene hybrid material |
| CN107490610B (en) * | 2017-09-05 | 2019-09-27 | 济南大学 | A kind of chirality MOF- graphene hybrid material and its preparation method and application |
| CN108441982B (en) * | 2018-02-13 | 2020-09-18 | 浙江工业大学 | Preparation method of graphene/metal organic framework composite fiber |
| CN108770328B (en) * | 2018-07-16 | 2020-02-18 | 安徽大学 | MOF-derived composite microwave absorbent and preparation method thereof |
| CN109270140B (en) * | 2018-11-01 | 2021-03-26 | 安阳师范学院 | Preparation method and application of electrochemical sensor made of high-dispersion graphene/Zn-based metal organic framework composite material |
| CN109916973B (en) * | 2019-02-28 | 2020-05-19 | 华中科技大学 | Ball-milled graphene-MOFs composite material, and preparation and application thereof |
| CN110335762A (en) * | 2019-07-09 | 2019-10-15 | 南京邮电大学 | A kind of preparation of GO/Cu-HHTP composite material and its application in electrochemical energy storage |
| CN110387099A (en) * | 2019-07-18 | 2019-10-29 | 华南理工大学 | A kind of tealeaf residue graphene-CuCeMOF-PVB composite material and preparation method and application |
| CN110385034A (en) * | 2019-07-25 | 2019-10-29 | 江苏中科睿赛环境工程有限公司 | A kind of the exhaust gas joint processing system and combination treatment method of biology-adsoption catalysis |
| CN111821952A (en) * | 2020-07-15 | 2020-10-27 | 广东石油化工学院 | Preparation method of polyvinylidene fluoride/graphene oxide/metal organic framework three-phase composite material |
| CN113311036B (en) * | 2021-05-23 | 2024-01-12 | 山东化工职业学院 | MOFs/GO composite gas-sensitive material and preparation method and application thereof |
| CN114204048A (en) * | 2021-11-25 | 2022-03-18 | 华北电力大学 | Iron/cobalt/nitrogen/co-doped porous carbon nanoparticle composite material derived from graphene oxide coated ZIF-67 |
| CN114249946B (en) * | 2021-12-07 | 2023-11-14 | 西华大学 | Preparation method of ultralow VOC polypropylene-based automobile special material |
| CN114425365B (en) * | 2022-01-29 | 2024-04-26 | 重庆交通大学 | Preparation method of defect-rich Mn-Co metal oxide catalyst |
| CN115554986B (en) * | 2022-09-20 | 2023-08-25 | 华南理工大学 | Metal organic framework material with efficient adsorption effect and preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2363399B2 (en) * | 2010-01-20 | 2012-05-25 | Universidad Politécnica De Valencia | CATALYST FOR SELECTIVE OXIDATION OF HYDROCARBONS. |
| CN101869851A (en) * | 2010-05-14 | 2010-10-27 | 东北师范大学 | Supported polyoxometallate crystalline catalyst and preparation method thereof |
-
2013
- 2013-08-30 CN CN201310390975.5A patent/CN103432997B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN103432997A (en) | 2013-12-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103432997B (en) | Cu base organic backbone-graphene oxide composite porous material and preparation method thereof | |
| CN107629076B (en) | A kind of ordered big hole metal organic frame monocrystalline and preparation method thereof | |
| CN107175125B (en) | Activation method of MOFs base oxygen reduction electrocatalyst | |
| CN106905536B (en) | Method for rapidly synthesizing hierarchical pore ZIF-8 material | |
| CN102335592B (en) | Metal organic skeleton-graphite oxide nano composite adsorption material and preparing method thereof | |
| CN104138746A (en) | Copper-based metal-organic framework porous material and preparation method and application thereof | |
| CN107715843B (en) | Method for rapidly synthesizing mesoporous and microporous ZIF-8 material at normal temperature | |
| CN108404868B (en) | Based on doping of NH by alkali metal cations2-MIL-125(Ti) material and preparation method thereof | |
| CN111375385B (en) | Preparation method and application of bimetallic organic framework adsorbent | |
| CN103694469A (en) | Sulfide functionalized covalent organic frame material and synthesis method thereof | |
| CN104415737A (en) | Magnesium-based metal organic framework material for methane-nitrogen adsorption separation and preparation | |
| CN104193768A (en) | Small and medium dual-hole HKUST-1 material and preparation method and application thereof | |
| CN103044463A (en) | Method for high-efficiency preparing zeolite imidazole metal organic frame ZIF-90 | |
| CN104226256A (en) | Spherical forming Cu base metal organic skeleton-graphene oxide composite material and preparation method of spherical forming Cu base metal organic skeleton-graphene oxide composite material | |
| CN101708459B (en) | Method for preparing ordered mesoporous organic titanium phosphonate hybrid material and application thereof | |
| CN104128163A (en) | Preparation method of microporous-mesoporous MIL-101 material and application thereof | |
| CN109369922B (en) | Method for rapidly synthesizing hierarchical pore ZIF-67 material at normal temperature by using cationic template | |
| CN110227456A (en) | MOFs derives two-dimensional multistage hole Cu/C composite material and preparation method | |
| Liu et al. | Homochiral metal phosphonate nanotubes | |
| Zhang et al. | Green and rapid preparation of hierarchically porous metal–organic zeolites and simulation of their growth | |
| CN115536857A (en) | Zinc-organic framework material for selectively adsorbing carbon dioxide and synthesis method | |
| CN108538618A (en) | A kind of porous ZnO-C composite and its preparation method and application | |
| CN112250877B (en) | Hierarchical pore ZIF-67 material and synthetic method thereof | |
| CN110124615B (en) | Porous carbon-based adsorbent for gas adsorption and preparation method thereof | |
| CN104592255B (en) | A kind of method repairing cuprio-metallic organic framework porous material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |